US11299507B2 - Synthesis and use of oxa-spirodiphosphine ligand - Google Patents

Synthesis and use of oxa-spirodiphosphine ligand Download PDF

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US11299507B2
US11299507B2 US16/770,087 US201816770087A US11299507B2 US 11299507 B2 US11299507 B2 US 11299507B2 US 201816770087 A US201816770087 A US 201816770087A US 11299507 B2 US11299507 B2 US 11299507B2
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ligand
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US20200308206A1 (en
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Xumu Zhang
Genqiang CHEN
Jiaming Huang
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Shenzhen Catalys Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • B01J31/249—Spiro-condensed ring systems
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
    • B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
    • B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/821—Ruthenium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Definitions

  • the present invention relates to the field of asymmetric catalysis, and particularly to the synthesis of a novel oxa-spirodiphosphine ligand.
  • the compound can be used as a chiral ligand in asymmetric catalytic reactions and has high potential of use in the field of asymmetric catalysis.
  • asymmetric catalysis has achieved rapid development.
  • Various chiral ligands have been synthesized and used in the field of asymmetric catalysis.
  • the diphosphine ligand is one of the ligands that are most widely used and extensively studied so far. It exhibits excellent activity and enantioselectivity in asymmetric hydrogenation, asymmetric hydroformylation, asymmetric Pauson-Khand reaction, asymmetric Heck reaction, asymmetric cycloaddition reaction, and asymmetric cycloisomerisation reaction, etc.
  • DIOP synthesized by the Kagan's team, BINAP developed by the Noyori's team, and DIPAMP ligand developed by the Knowles' team are milestones in the development history of diphosphine ligands. They have been widely used in academia and industry. Then various chiral diphosphine ligands were synthesized, for example, SegePhos, DifluoPhos, SynPhos, C n -TunePhos, TangPhos, DuanPhos, ZhangPhos, SKP, SDP, and SFDP.
  • the present invention provides an oxa-spirodiphosphine ligand having a structure of general Formula (I) below:
  • R 1 and R 2 are independently alkyl, alkoxy, aryl, aryloxy, or hydrogen, in which R 1 , R 2 , R 3 and R 4 may or may not form a ring; R 1 and R 6 are independently alkyl, aryl, or hydrogen; and R 1 and R 8 are alkyl, benzyl, or aryl.
  • alkyl is preferably methyl, ethyl, propyl, butyl, or the like.
  • alkoxy is preferably methoxy, ethoxy, propoxy, butoxy, or the like.
  • the aryl is preferably phenyl that is unsubstituted or substituted with alkyl or alkoxy as defined above.
  • the aryloxy is preferably methoxyphenyl, ethoxyphenyl or the like.
  • R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are all hydrogen.
  • the oxa-spirodiphosphine ligand is the ( ⁇ )-oxa-spirodiphosphine ligand, the (+)-oxa-spirodiphosphine ligand, or the ( ⁇ )-oxa-spirodiphosphine ligand.
  • the oxa-spirodiphosphine ligand is a compound having a structure below:
  • Ar is alkyl, benzyl or aryl; and most preferably Ar is phenyl, or phenyl substituted with alkyl or alkoxy.
  • alkyl and alkoxy are as defined above.
  • Another object of the present invention is to provide a method for synthesizing the compound by the following route:
  • Another object of the present invention is to provide use of the compound in catalyzing asymmetric reactions including hydrogenation reaction, hydroformylation reaction, hydrosilation reaction, hydroboration reaction, hydroxylation with hydrogen peroxide, hydroamination reaction, hydrocyanation reaction, isomerization and formylation reaction, hydroaminomethylation reaction, transfer hydrogenation reaction, allylation reaction, olefin metathesis reaction, cycloisomerization reaction, Diels-Alder reaction, asymmetric coupling reaction, Aldol reaction, Michael addition reaction, asymmetric epoxidation reaction, kinetic resolution and [m+n] cyclization reaction.
  • the diphosphine ruthenium acetate complex prepared from the compound has a high activity and an enantioselectivity of greater than 99% for the hydrogenation of unsaturated carboxylic acids in organic solvents.
  • diphosphine ruthenium acetate complex is a compound having a structure below:
  • R alkyl, fluoroalkyl or aryl; and alkyl and aryl as defined above are preferred.
  • the compound is used as a catalyst, and the reaction route is as follows:
  • R alkyl, fluoroalkyl or aryl; and preferably alkyl and aryl as defined above.
  • Another object of the present invention is to provide a bisphosphine ruthenium acetate complex, which has high activity and enantioselectivity for hydrogenation of unsaturated carboxylic acids in an organic solvent.
  • the bisphosphine ruthenium acetate complex is a compound shown below:
  • R alkyl, fluoroalkyl or aryl; and alkyl or aryl as defined above are preferred.
  • the oxa-spiro compound has central chirality, and thus include L-oxa-spirodiphosphine ligand and R-oxa-spirodiphosphine ligand.
  • the racemic spirodiphosphine ligand can be synthesized from racemic oxa-spirobisphenol as a raw material.
  • the present invention can be used as a chiral ligand in the asymmetric hydrogenation of unsaturated carboxylic acids. Its complex with ruthenium can achieve an enantioselectivity of greater than 99% in the asymmetric hydrogenation of methyl-cinnamic acid.
  • FIG. 1 is a schematic view showing the preparation of various chiral compounds according to the present invention, and the corresponding conversion rates and enantioselectivity ee.
  • the conversion rate of various substances in the presence of 6a is shown in FIG. 1 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • General Health & Medical Sciences (AREA)
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  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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  • Nitrogen Condensed Heterocyclic Rings (AREA)
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US20220185835A1 (en) * 2020-06-05 2022-06-16 Shenzhen Catalys Technology Co., Ltd Synthesis and use of oxa-spirodiphosphine ligand

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CN115304617A (zh) * 2021-05-08 2022-11-08 惠州凯特立斯科技有限公司 一种大位阻氧杂螺环二酚及其双膦配体的合成方法
CN115724781A (zh) * 2021-08-30 2023-03-03 凯特立斯（深圳）科技有限公司 一种合成乌帕替尼关键手性中间体的方法
CN116655693A (zh) * 2023-04-28 2023-08-29 凯特立斯（深圳）科技有限公司 氧杂螺环双膦配体的制备方法及其应用

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US20210340168A1 (en) * 2020-04-30 2021-11-04 Shenzhen Catalys Technology Co., Ltd. OXA-SPIRODIPHOSPHINE LIGAND AND METHOD FOR ASYMMETRIC HYDROGENATION OF alpha, beta-UNSATURATED CARBOXYLIC ACIDS

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CN1238361C (zh) * 2003-02-21 2006-01-25 南开大学 螺环双膦配体
CN1562926A (zh) * 2004-04-14 2005-01-12 南开大学 新型螺环双膦配体及其在不对称催化氢化中的应用
JP5454756B2 (ja) * 2008-08-26 2014-03-26 国立大学法人 千葉大学 ジホスフィン化合物、その遷移金属錯体およびその遷移金属錯体を含む触媒並びにホスフィンオキシド化合物及びジホスフィンオキシド化合物
WO2017135897A1 (fr) * 2016-02-02 2017-08-10 Agency For Science, Technology And Research Catalyseur pour la carbonylation d'alcènes

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US20210340168A1 (en) * 2020-04-30 2021-11-04 Shenzhen Catalys Technology Co., Ltd. OXA-SPIRODIPHOSPHINE LIGAND AND METHOD FOR ASYMMETRIC HYDROGENATION OF alpha, beta-UNSATURATED CARBOXYLIC ACIDS

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US20220185835A1 (en) * 2020-06-05 2022-06-16 Shenzhen Catalys Technology Co., Ltd Synthesis and use of oxa-spirodiphosphine ligand
US12071444B2 (en) * 2020-06-05 2024-08-27 Shenzhen Catalys Technology Co., Ltd Synthesis and use of oxa-spirodiphosphine ligand

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EP3730502B1 (fr) 2024-10-02
WO2019153203A1 (fr) 2019-08-15
EP3730502A1 (fr) 2020-10-28
ES3005385T3 (en) 2025-03-14
EP3730502A4 (fr) 2021-02-24

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